Process and treating bath for the production of colored photographic pictures



Patented May 16, 1944 UNITED s A'ri;

PROCESS AND TREATING BATH FOR THE PRODUCTION OF COLORED PHOTO- GRAPHIC PICTURES.

Hollywood, Calif.,

Bela Gaspar,

assignor to,

Chromogen, Incorporated, a corporation of Nevada No Drawing. Original application December 13,

1937, Serial No.

179,591. Divided and this applicati'on September 25, 1941, Serial No..412 ,342. In Great Britain- December 14, 1936 35 Claims.

In my earlier p'atentsa process has been described. for the production. of dyestuff images from diffusely dyed silver images. Thus, for ex.- ampldaccording to my U. S. Patent No. 2,020,7?5, dated November 12, 1935 the production. of such, dyestufi images is performed by treating the diffusely dyed silver image with solutions which destroy the dye locally. in the presence of the metal deposit of the photographic image.- At the same time the silver ispartiallyor totally. converted into a silver compound. Individual. cases, in which the destruction of the dye can' be accelerated by the addition of certain substances, have been described in the above referred to p t ts It has been found that the effectiveness of the dye destroying solutions described in my U. S. Patent No. 2,020,775 and of the other dye d'estroyi-ng baths which were found. to be applicable in the process, can be accelerated by a-great number of substances other than those heretofore known. A- large number of the substances added in accordance with this invention'yie-ld' treating solutions which Work in a much more effective manner, e. g.- inmuch shorter time; or in far smaller concentration, than theproducts previously proposed as accelerators, In view of the great; effectiveness of the additions much smalleramountsof these accelerating substances are sufficient;

The present application is a divisionof my;application Serial N0.- lions-i filed December 13, 1937 (now Reissue Patent No. 22,308); wherein is-claimedthe use of reducible organic substances 'se'lected'trom the group of those reduciblesubstances; the: reduction products of which are reeoxidizable during the treatmentof a: dyed silver image to, the original reduciblejsubstanc'e;

According to the present invention reducible ess of producing a photographic dye image in a photdg'raphic' emulsion uniforirily dyed by" an azo-d'ye andcomprising a developed silver image.

For convertingthe sil'ver into a dye image a such a type as isreducibleto form a reduction product which is reoxidizable under the conditions of the treating bath.

in order to' illustrate the present. invention severaiexamples are set forth as follows:

organic dyes are used' as accelerators in-the procdescribed in my Example 1 to which 0.2% auraminehas been added. Thistreatment destroys the dye at the places. of the metal deposit within a considerably shorter time than if the hydrochloric acid bath was used with out the auramine. After thetreatmen-t with the dye-destroying bath the. silver image is 7 converted into a silver salt and fixediout;

Example 2 A photographic silver image uniformly dyed with Chlorantine- Light Green BB (a dye furnished by the CIBA, Gesellschaft fur Chemische Industrie, Basel; Switzerland) is treated with an 11%: hydrochloric. acid solution towhich 0.2% sodium indigo sulfonate are added. This addition accelerates the destruction of the dyeconsiderably. s I

r Example 3 A silver image, as; used in Examples 1' or 2, is treatedwith an 11% hydrochloric acid solution to whijch 0.2%; of Alizarine Red S 'has'b'een" added. The addition renders the dyedestruction more rapid.

Example 4}- 0.2% of N-ethyl-benzthiazol-carbocyanine iodide are used as an addition, to the1l% hydrochloric acid solution-and the solutionis employed for. treating silver imagesdye'd with the dyes used in Examples ,1 and 2.

Other examples of dyeedestroying baths are p U. S. PatentNo. 2,020,775 such, for exam le, assolutions oi thiocarbamide and the parent application which matured into Patent 2,210,118 on January 13, 1942, and reissued as Patent Re. 22,308, dated May 11, 1943, discloses the use of. dye-destr oyin'gpbaths} comprising hydrobromic acid, sodium hypos'ulphite, 20% sodium chloride and hydrochloric; acid, 20% maglnesium chloride. and hydrochloric acid in addition to a' hydrochloric acid, solution by itself. The dyesmay be insoluble azo-dyes as well as az'o-dyes that are soluble in water. In using insoluble azo-dyes which do not bleach readily with thedye-destroying solutions used alone, the difference in speed ismore evident than if dyes are employed which are bleached out in-shorter times in a dye-destroying bath without admixture. Mention should, however, be made of the fact that the application of the admixtures has certain advantages even in the case of easily soluble and easily bleachin dyes, such as a shortening of the time of treatment and thereby a decrease of the detrimental effect on the layers.

The following dyes may be cited as further examples of accelerators: methyl violet B; alizarine-red-Agfa; dimethylaminostyryl dimethylthiazol-N-methyliodide; 6, methoxy-pseudocyanine N-ethyl-iodide; N-ethyl-G, methoxy-tliiocarbocyanine-iodide; (3) -nitrostyryl quinolini um-N-ethyl-ethylsulphonate; (3) nitrostyryl benzthiazol-ethyl-sulphonate; ('3) -sulpho-styrylpseudo-thiohydantoine; styryl-quinolinium-ethyl sulphonate; (4) -dimethylamino-styryl rhoda nine. They may be used as additions to an 11% hydrochloric acid solution and used for the'local destruction of the dyes referred to in the above examples. 0.2% ofthedyes may be used.

The above examples are illustrative of methine and anthraquinone dyes which have been found effective as accelerators in dye destruction baths and in carrying on the process of the present invention. As will be seen, some of. the above dyes are sensitizing dyes or desensitizing dyes. The accelerating effect appears to be in no direct proportion to the sensitizing properties but, on the contrary, to be based mainly on the fact that these dyes are substances which can be easily hydrated and which form reversible systems with their reduction products. The particular chemical structure, such as the presence of :0 or C=S groups in a carbocyclic or heterocyclic nucleus or in the quinone configuration may be responsible for the particular acceleration properties. Some of the dyes "referred'to above are typical examples of vat dyes and dyes capable of forming leuco compounds by reduction, which leuco compounds can be re-oxidizedeasily to the original dye. I i i WhatIclaimisz- 1. A treating bath for producing a photographic dye image in a photographic emulsion uniformly dyed byan azo-dye and also comprising a developed silver image comprising hydrohalic acid and a small amount oi fan organic dye which is reducible and the reduction products of which are reoxidizable during the production of saiddye image to the original reducible organic dye, the composition of said treating bath being such that the reduction products are reoxidizable during the production of said dye image and said treating bath being initially substantially free of reducing substances capable of being converted into said reducible substance by oxidation. I

2. A treating bath for producing a photographic dye image in a photographicemulsion uniformly dyed by an azo-dye and also comprising a developed silver image, comprising hydrohalic acid and a small amountof a methine dye which is reducibleduring the production of the image.

3. A treating bath for producing a photographic dye image in a photographic emulsion uniformly dyed by an azo-dye and also, comprisinga developed silver image, comprising hydrohalic acid and a small amount of an anthraquinone dye which is reducible during the production of the image. 1 g

4. A treating bath for producing a photographic dye image in a photographic emulsion uniformly dyed with an azo-dye and also comprising a developed silver image, comprising a substance capable of forming complex silver compounds and which acts to selectively destroy said azo-dye by' reduction in the presence of said silver image and a small amount of an organic dye which is reducible and the reduction products of which are reoxidizable during the production of said image to the original reducible organic dye, the composition of said bath being such that the reduction products of said organic dye are reoxidizable during the production of said dye image and said bath being initially substantiall free of reducing substances capable of being converted into said reducible dye by oxidation.

5. A treating bath for producing a photographic dye image in a photographic emulsion uniformly dyed with an azo-dye and also comprising a developed silver image, comprising a substance capable of forming complex silver compounds and which acts to selectively destroy said azo-dye by reduction in the presence of said silver image and a small amount of an anthraquinonedye which is reducible during the production of said dye image.

6. A treating bath for producing a photographic dye image in a photographic emulsion uniformly dyed with an azo-dye and also comprising a de-" veloped silver image, comprising a substance capable of forming complex silver compounds and which acts to selectively destroy said azo-dye by reduction in the presence of said silver image and a small amount of a methine dye which is reducible during the production of said dye image.

7. A treating bath for producing a photographic dye image in a photographic emulsion uniformly dyed with an azo-dye and also comprising adeveloped silver image, comprising a substance capable of forming complex silver compounds and which acts to selectively destroy said azo-dye by reduction in the presence of said silver image and a small amount of a reducible vat dyewhich is reducible during the production of said dye image.

8. A treating bath for producing a photographic dye image in a photographic emulsion uniformly dyed with an azo-dye and also comprising a developed silver image, comprising asubstance capable of forming complex silver compounds and which acts to selectively destroy said'azo-dye by reduction in the presence of said silver image and a small amount of a vat dye capable of forming aleuco-compound during the production of said dye image.

9. In the process of producing photographic dye images from silver images uniformly dyed by an azo-dye, the step of treating said silver images with a solution containing a substance capable of selectively destroying said azo-dye by reduction in the presence of a photographic silver image and comprising a small amount of an organic dye which is reducible and the reduction products of which are reoxidizable during the production of said dye images to the original organic dye, the composition of said solution being such that the reduction products of said organicdye are reoxidizable during the treatment of said silver images and said solution being substantially free of reducing substances capable of being converted into said reducible dye by oxidation.

10. In the process of producing photographic dye images from silver images uniformly dyed by an azo-dye, the step of treating said silver images with a solution containing a substance capable of selectively destroying said azo-dye by reduction in the presence of a photographic silver image and comprising. a small amount, 0.5a reducible methine dye.

11. In the. process of producingphotographic dye images from silver images uniformly dyed by an azoedye, the. step. of treating said silver images with a solution containing a substance capable of selectivelydestroying said azo-dyev by reduction in the presence of a. photographic silver image and comprising a small. amount of a reducible anthraquinone dye.

12'. A'process of producing a photographic dye image in a photographic emulsion uniformly dyed by an and-dye and comprising a developed metal image, which consists. in treating the said developed metal image with a solution containing an agent which is non-destructive with. respect to the. dye, but reacts with the said metal to oxidize it. and substantially.simultaneously to form a reducing substance which destroys said azo-dye at the points. of the metal image, said solution further containing aismall amount. ofpan organic dye which is. reducible and: the reduction prodnets of which are reoxidizableduringthe production of: said image. to the original reducible organic dye, thecomposition of said batlrbeing such that the reduction products of saidgorganic dye are reoxidizable during he pr duction of saiddye: image and said bath, being initially substantially free of reducing substances capable of being converted into said reducible dye by oxidation.

13. A process of producing a photographic dye image in. a. photographic emulsion uniformly dyed by an azoedye. and comprisin dev lope metal image, which consists in treating the said developed: metal-image with a solution containing an agent which isv non-destructive with respect to thedye. but. reacts, with the said; metal to oxidize. it and. substantially simultaneously to ,forma reducing substance which destroys said azodye at, the points: of, the metal image, said solution further containing asmall amount of a methine dye which is; reducible during the production of said, dye image.

14. A, process. of producing; a. photographic dye im e in apho o r phi muls i ormly yed by an azo-dye and comprising a developed metal image, which consists intreating' the said devel p d metal ma e,- with, a solu ion: co aini g an agent which; is non-destructive, with respect to the dye} but reactswith the said metal to ox-idize it and: substantially simultaneously to form a reducing; substance which destroys said azo-dye at the points of the metal image, said solution further containing a small amount of; an anthraquinonc dye which;v is reducible, during the p oduc i n of: said dy ima e.

15:. A treating; bath for, producing a photoraphs; ma e ma phot r phic. mulsion ni o mly yed by n. azoy nd so. comp sme veloped Silver ma m ri i hydr chloric acid and a small amount of an organic dye; which is: reducible and the reduction products of, which are reoxidizable during the production of said image to; the original reducible; organic dye, the; composition. of said bath beingsuchthat the reduction products of said organic dye are reoxidizable during the production; of} said dye image and said th in nitia y ubs a t a ly freeofrcducingsubstances capable of being, converted, into said reducible dyeby oxidation.

6: A rea in a h r p o u in a p oaphi re ma e 1 1a. pho o r phi emulsio uni o lv y dbr n z ya nd a so ompris the a deve oped silv r ma e. mpr sin hy o- Q JlQUQTQQiG 3 1. mal mpuo at m thineoy which is reducible during the production, of the uniformly dyedby an azo-dye and also comprising a developed silver image, comprising hydrochloric acid and a small amount of an anthraquinone dye which is reducible during the pro.- duction of the. image.

l8. In'the process of producing photographic dye images from silver images uniformly dyed'by an-azo-dye, the step of treating said silver images with a solution containing a substance capable of selectively destroying said azo-dye by reduction in the presence of a photographic silver image and comprising a small amount of a vat dye.

19. A processof producing a photographic dye image in a photographic emulsion uniformly dyed by an azordye and; also comprising a silver image, which comprises the step of treating said silver image with a; solution comprising a substance which is capable of forming complex silver compounds and which acts to selectively destroy said azo-dye by reduction-in, the presence of said silver image and a small amount of a methine dye which is reducible during the production of said dye image.

2.0; A process of producing a photographic dye image in. a photographic emulsion uniformly dyed by an aZo-dye andalso comprising a silver image, which comprises the step of treating said silver image with a solution comprising a substance which is capable of forming complex silver compounds. and which acts to selectively destroy said azo-dye by reduction in the presence of said, silver image and a small amount of an anthraquinone dyewhich; is reducible during the production. of aid yc mase.

21;. A; process of producing-a photographic dye ima e a ph to raphi mu s nif m y y by anaao-d-ye and also comprising a silver image. whichcorn-prises-the step of treating said silver image with. a: solution comprising a. substance- Which is capable of. forming com-plexsilver compounds and which acts to selectively destroy said azo-dye by reductionin the presence of said silver image and a smallamount of a vat dye which is reducible duringtheproduction of said dye image.

22. A process of producing aphotographic dye image in a photographic emulsion uniformly dyed by an azo-dyeandalso: comprising a silver image, which comprises the step of treating said silver image with a solution: comprising a substance which capable of forming complex silver compoundsand which acts to selectively destro said azo-dye by reductionin the presence of'said silver image and a smallamountof a reducible dye selected from the group consisting of anthraquinone, methine and. vat dyes.

2 3. In, the process of producing photographic dye images from silver-images uniformly dyed by an-azo-dye, thestepof treating said silver images with asolution containing a substance capable of selectively destroying said azo-dye by reduction-in the presenceof aphotographic silver image and comprising a. small amount of a reducible dyeselected from the. group consisting of anthraquinone, methineandgvat dyes.

24. A process of producing a photographic dye image'in a photographic. emulsion uniformly dyed byranazoedye and comprising a. developed metal image, whichconsists in treating the said developed metal. image with a. solution containing an agent which isnon destructive with respect to the dye, but reacts with. the said metal to oxidize it and substantially simultaneously to form a reducing substance which destroys said azo-dye at the points of the metal image, said solution further containing a small amount of a reducible dye selected from the group consisting of an thraquinone, methine and vat dyes.

25. A treating bath for producing a photo-- graphic dye image in a photographic emulsion uniformly dyed by an azo-dye and also comprising a developed silver image, comprising hydrohalic acid and a small amount of an organic dye selected from the group consisting of anthraquinone, methine and vat dyes.

26. A treating bath for producing a photographic dye image in a photographic emulsion uniformly dyed with an azo-dye and also comprising a developed silver image, comprising a substance capable of forming complex silver compounds and which acts to selectively destroy said azo-dye by reduction in the presence of said silver image and a small amount of an organic dye selected from the group consisting of anthraquinone, methine and vat dyes.

27. A treating bath for producing a photographic dye image in a photographic emulsion uniformly dyed by an azo-dye and also comprising a silver image, comprising a substance which is non-destructive with respect to said azodye, but reacts with the silver to oxidize it and substantially simultaneously to form a reducing substance which destroys said azo-dye at the points of the silver image and also comprising a small amount of an anthraquinone dye which is reducible during the production of the dye image.

28. A treating bath for producing a photographic dye image in a photographic emulsion uniformly dyed by an azo-dye and also comprising a silver image, comprising a substance which is non-destructive with respect to said azo-dye, but reacts with the silver to oxidize it and substantially simultaneously to form a reducing sub-- stance which destroys said azo-dye at the points of the silver image and also comprising a small amount of a methine dye which is reducible during the production of the dye image.

29. A treating bath for producing a photographic dye image in a photographic emulsion uniformly dyed by an azo-dye and also comprising a silver image, comprising a substance which is non-destructive with respect to said azo-dye but reacts with the silver to oxidize it and sub stantially simultaneously to form a reducing substance which destroys said azo-dye at the points of the silver image and also comprising a small amount of a vat dye which is reducible during the production of the dye image.

30. A treating bath for producing a photographic dye image in a photographic emulsion uniformly dyed by an azo-dye and also comprising a silver image, comprising a substance which is non-destructive with respect to said azo-dye but reacts with the silver to oxidize it and substantially simultaneously to form a reducing substance which destroys said azo-dye at the points of the silver image and also comprising a small amount of an organic dye selected from the group consisting of anthraquinone, methine and vat dyes.

31. In a process of producing a'dye image in a photographic emulsion comprising a metal image and an azo-dye, the step of treating said azo-dye in the presence of said metal image with an agent which in the presence of said metal image is capable of selectively destroying said azo-dye by reduction, said treatment being carried out in thepresence of said metal image to the originalor-- ganic dye, said treatment with said reducible organic dye being initiated in the absence of reducing substances capable of being converted into said organic dye by oxidation and the conditions of said treatment being such that the reduction products ofsaid organic dye are reoxidizable duringsaid treatment of said azo-dye.

32. In a process of producing a dye image in-a' photographic emulsion comprising a silver image and an azo-dye, the step of treating said azo dye in the presence of said silver image with an agent which in the'presence of said silver image is capable of selectively destroying said azo-dye by reduction, said treatment being carried out in the presence of a quantity of a reducible organic dye suflicient to accelerate the selective destruc:

tion of said azo-dye, the said organic dye being selected from the group of those reducible organic dyes, the reduction products of which are reoxidizable during said treatment of said azo-dye in the presence of said silver image to the original organic dye, said treatment with said reducible organic dye being initiated in the absence of reducing substances capable of being converted into said organic dye by oxidation and the" conditions of said treatment being such that the reduction products of said organic dye are reoxidizable during said treatment of said azo-dye.

33. In a'pro'cess of producing a dye image in a photographic emulsion comprising a silver image and an azo-dye, the step of treating said azo-dye in the presence of said silver image with an agent which in the presence of said silver image is nondestructive with respect to the dyestuff, but reacts with the said silver to oxidize it and substantially simultaneously to form a reducing substance which destroys said'azo-dye at the points of the silver image, said treatment being carried out in the presence of a quantity of a reducible organic dye suificient to accelerate the selective destruction of saidazo-dye, the said organic dye being selected from the group of those reducible organic dyes, the reduction products of which are reoxidizable during said treatment of said azo-dye in the presence of said silver image to the original organic dye, said treatment being initiated with said reducible organic dye in the absence of reducing substances capable of being converted into said organic dyes by oxidation and the conditions of said treatment being such that the reduction products of said organic dye are reoxidizable during said treatment of said azo-dye. v

34. In a process of producing a dye image in a photographic emulsion comprising a silver image and an azo-dye, the step of treating said azo-dye in the presence of said silver image with a. solution comprising hydrohalic acid, said treatment being carried out in the presence of a quantity of a reducible organic dye suflicient to accelerate the selective destruction of said azo-dye, the said organic dye being selected from the group of those organic dyes, the reduction products of which are reoxidizable during said treatment of said azo+ dye in the presence of said silver image to the original organic dye, said treatment with said reducible organic dye being initiated in the absence of reducing substances capable of being converted into said reducible organic dye by oxidation and the conditions of said treatment being such that the reduction products of said reducible organic dye are reoxidizable during said treatment of said azo-dye.

35. In a process of producing a dye image in a photographic emulsion comprising a silver image and an azo-dye, the step of treating said azo-dye in the presence of said silver image with a solution comprising hydrochloric acid, said treatment being carried out in the presence of a quantity 01' a reducible organic dye sufiicient to accelerate the selective destruction of said azo-dye, the said organic dye being selected from the group of those organic dyes, the reduction products of which are reoxidizable during said treatment of said azodye in the presence of said silver image to the original organic dye, said treatment with said reducible organic dye being initiated in the absence of reducing substances capable of being converted into said reducible organic dye by oxi dation and the conditions of said treatment being such that the reduction products of said organic dye are reoxidizable during said treatment of said azo-dye.

BELA GAsPAR. 

